Fuel gas from solid carbonaceous fuels

ABSTRACT

This is a continuous partial oxidation process for producing fuel gas or synthesis gas from solid carbonaceous fuels. In the process, two separate solid carbonaceous slurry feed streams (with the liquid vehicle being water in one slurry stream and liquid hydrocarbon fuel in the other) along with a separate stream of free-oxygen containing gas which is interposed between said slurry streams, are simultaneously introduced into a reaction zone of a free-flow noncatalytic gas generator where the three streams impinge and mix together to form an atomized dispersion that reacts by partial oxidation at an autogenous temperature in the range of about 1,500* to 3,500*F. and a pressure in the range of about 1 to 250 atmospheres. The effluent gas stream from the reaction zone is split into two streams which are separately cooled and cleaned to produce two separate gaseous streams one gaseous stream saturated with water and the other gaseous stream containing less than 15 mole % water. By the subject mixed mode operation, the weight ratios of water to fuel, oxygen to fuel, and liquid hydrocarbon fuel to total solid fuel may be lowered. This provides a more suitable, and economical gas generator operation.

United States Patent Crouch 1 Dec. 30, 1975 FUEL GAS FROM SOLIDCARBONACEOUS ducing fuel gas or synthesis gas from solid carbona- FUELSceous fuels. In the process, two separate solid carbonaceous slurry feedstreams (with the liquid vehicle [75] Inventor. William B. Crouch,Whittier, Calif. being water in one slurry stream and liquid hydrocar[73] Assignee: Texaco Inc., New York, NY. bon fuel in the other) alongwith a separate stream of [22] Filed: Sept. 26,1974 free-oxygencontaining gas which is interposed between said slurry streams, aresimultaneously intro- [21] Appl. No.: 509,375 duced into a reaction zoneof a free-flow noncatalytic gas generator where the three streamsimpinge and mix together to form an atomized dispersion that re- [52] Cl48/201 48/202 cg acts by partial oxidation at an autogenous temperature2 in the range of about l,500 to 3,500F. and a pres- [51] Int. Cl. C01B2/14, C10J 3/16 Sure in the range of about 1 to 250 atmospherea The [58]Field of Search 48/201, 202, 210, 215,

48 /197 R effluent gas stream from the reaction zone is split into twostreams which are separately cooled and cleaned [561 235:3?23.12;sfittest:52:12:2522:22::

UNITED STATES PATENTS stream containing less than 15 mole water. By the3,607,157 9/1971 Schlinger 48/202 subject mixed mode operation, theweight ratios of 3,715,195 2/1973 Tassoney 61 48/197 R water to fuel,oxygen to fuel, and liquid hydrocarbon 3,715,301 2/1973 Tassoney et al.48/202 X fuel to total Solid fuel may be lowered This provides a PrimaryExaminerR. E. Serwin Attorney, Agent, or FirmT. H. Whaley; C. G. Ries;Albert Brent [57] ABSTRACT This is a continuous partial oxidationprocess for promore suitable, and economical gas generator operation.

6 Claims, 2 Drawing Figures He. Patent Dec. 30, 1975 FUEL GAS FROM SOLIDCARBONACEOUS FUELS 7 BACKGROUND OF THE INVENTION 1. Field of theInvention This invention relates to a continuous process for themanufacture of fuel and synthesis gas from solid carbonaceous fuels.

2. Description of the Prior Art Because of increasing oil prices anddecreasing supplies of natural gas, it is now necessary to use othernatural fuel resources which were previously uneconomical. While largedeposits of comparatively low cost coal and oil shale exist in thiscountry, these solid carbonaceous materials may not be in a convenientform for many uses. Often these materials contain excessive amounts ofsulfur compounds which limit their use as a fuel. In the subjectimproved process, slurry streams of a solid carbonaceous fuels may beburned more efficiently than previously in a synthesis gas generator.

SUMMARY By the subject invention, two different and separate slurrystreams of solid carbonaceous fuels are simultaneously brought togetherin a single free-flow gas generator where by partial oxidation they areefficiently converted into synthesis gas or into a clean fuel gas whichmay be burned without contaminating the environment.

The two pumpable slurry reactant streams are simultaneously passedthrough a double annulus type burner mounted in a gas generator. Oneslurry stream comprises a solid carbonaceous fuel with water as theliquid carrier and the other slurry stream comprises a solidcarbonaceous fuel with a liquid hydrocarbon fuel as the carrier. Oneslurry stream is passed through the central conduit of the burner whilethe other slurry stream is passed through the outer annulus of theburner. Simultaneously, a reactant stream of free-oxygen containing gasis passed through the intermediate annulus passage of the burner therebyflowing between the other two streams. The three reactant streams areintroduced simultaneously into the refractory lined reaction zone of thefree-flow noncatalytic gas generator where they impinge, atomize, andmix together. The velocity of each of the slurry streams is in the rangeof about 1 to 500 feet per second. The velocity of the free oxygencontaining gas is in the range of about 100 feet per second to sonicvelocity.

Partial oxidation reaction takes place in the reaction zone of the gasgenerator at an autogenous temperature in the range of about l,500 to3,500F. and a pressure in the range of about 1 to 250 atmospheres. Theeffluent gas leaving the gas, generator is split into two streams. Thefirst split stream of gas is cooled in a waste-heat boiler to producesteam. This cooled gas stream is then scrubbed with liquid hydrocarbonfuel or optionally water to remove entrained particulate solids.Optionally, by conventional gas purification procedures, acid-gases maybe removed to produce a clean 2 By the subject invention, it wasunexpectedly found that readily available solid carbonaceous fuels maybe more economically converted into a clean fuel gas having a grossheating value in the range of about to 400 BTU per SCF or into synthesisgas. Improved performance may be shown by reduction in the followingweight ratios: water to fuel, oxygen to fuel, and liquid hydrocarbon tototal solid fuel.

BRIEF DESCRIPTION OF THE DRAWING DESCRIPTION OF THE INVENTION By meansof the subject process, two gaseous streams each comprising principallyhydrogen and carbon monoxide, and optionally at least one member of thegroup carbon dioxide, water vapor, methane, nitrogen, argon,

TABLE I Product Gas H, 8.0 to 60.0 CO 8.0 to 70.0 CO, 1.0 to 50.0 I'I;O2.0 to .50.0 CH, 0.0 to 30.0 COS 0.0 to 0.7 I-I,S 0.0 to l .0 N, 0.0 to85.0 A 0.0 to 2.0

The solid carbonaceous fuel employed in the subject process gas isselected from the group consisting of coal, coke from coal, coal char,petroleum coke, oil shale, tar sands, pitch, particulate carbon, andmixtures thereof. With the exception of particulate carbon which has aparticle size of less than 10 microns, all of the other solidcarbonaceous fuels are preferably ground to a particle size so that 100%of the material passes through an ASTM E 11-70 Sieve DesignationStandard 425 um (Alternative No. 40) and at least passes through an ASTME 1 1-70 Sieve Designation Standard 75 pm (Alternative No. 200) 1,000 um1 mm.

The coal may be any type eg anthracite, bituminous and lignite. Cokefrom coal is the strong porous residue comprising carbon and mineral ashformed when coal e.g. bituminous is heated in the absence of air in acoke oven. Coal char may be made by the pyrolysis of coal ata'temperature in the range of about 600 to l,600F. with or without thepresence of air, hydrogen or synthesis gas. For example, char may beproduced in a fluidized bed retort-see coassigned U.S. Pat. No.3,715,30l. Petroleum coke consists of dehydrogenated and condensedhydrocarbons of high molecular weight in the form of a matrix ofconsiderable physical extent. 1t principally comprises carbon andcontains dispersed throughout a very minor amount of petroleum-basedasphaltic-like compounds. Raw petroleum coke suitable for use as astarting material in the process of this invention may be produced bythe delayed coking process or by a similar process for converting heavyresidual fuel oil into gasoline, gas oil, and coke. A typical delayedcoking process is described in Kirk-Othmer Encyclopedia of ChemicalTechnology, 2nd Edition, Vol. 15, Inter-Science Publisher 1968, pages20-23. Calcined petroleum coke and fluid coke are also suitable as astarting material. Pitch is a black amorphous solid or semi-solidresidue obtained from the distillation of tars and tar products.Particulate carbon or free carbon soot may be found entrained in theeffluent gas stream from the partial oxidation gas generator in theamount of about to weight percent (basis weight of carbon in the fuel).This particulate carbon is both oleophilic and hydrophobic. It has anOil Absorption No. of more than 1, and usually one gram of particulatecarbon will absorb 23 cc of oil.

Some typical solid carbonaceous fuels are described The second reactantslurry stream comprises a solid carbonaceous fuel-water pumpable slurryhaving a solids content in the range of about 30 to 65 weight percentand preferably about 45 to 60 wt. This second slurry feedstream isprepared by mixing together a solid carbonaceous fuel or mixturesthereof as previously described with water.

The third reactant stream comprises a free-oxygen containing gasselected from the group consisting of air, oxygen-enriched air, i.e. atleast 22 mole oxygen, and substantially pure oxygen i.e. at least 95mole oxygen (the remainder comprising N, and rare gases). Substantiallypure oxygen is preferred in order to reduce the amount of nitrogen andother gaseous impurities in the product gas.

The three reactant streams previously described are introducedsimultaneously into the reaction zone of a conventional free-flow gasgenerator preferably by way of a double annulus burner. The gasgenerator is free from packing and catalyst. It is a vertical steelpressure vessel lined on the inside with refractory, such as describedin coassigned U.S. Pat. No. 3,097,081. A suitable multiple annulusburner is shown in coassigned U.S. Pat. No. 3,705,108. However, thefeedstream and further in Table II. 25 velocities for the subjectprocess differ from those dis- TABLE II TYPICAL SOLID CARBONACEOUS FUELSBituminous Coal Petroleum Particulate Coal Coal Coke Char Coke CarbonProximate Analysis, Wt.% (dry) Volatile 38.6 2.0 3.5 5.0 3.0 MatterFixed Carbon 50.0 88.0 76.4 94.3 93 Ash 11.4 10.0 20.1 0.7 4.0 TOTALS100.0 100.0 100.0 100.0 100.0 Ultimate Analysis, Wt.% (dry) C 67.2 78.976.8 88.4 95.2 H I 5.2 7.5 1.4 7.0 1.6 N 1.3 1.1 1.2 2.1 0.2 S 3.8 1.13.1 1.5 0.6 O 11.1 7.2 0.1 0.4 Ash 1 1.4 4.2 17.4 0.6 2.4 TOTALS 100.0100.0 100.0 100.0 100.0

The solid carbonaceous fuels that are used in the subject process arefirst ground to the proper size and mixed with a liquid vehicle toproduce a pumpable slurry. Thus, a first reactant slurry stream maycomprise a solid carbonaceous fuel-liquid hydrocarbon fuel slurry havinga solids content in the range of about to 65 Weight percent andpreferably about to 60 wt. This first slurry feedstream is prepared bymixing together a liquid hydrocarbon fuel with a solid carbonaceous fuelselected from the group consisting of coal, coke from coal, coal char,fluid or delayed petroleum coke, calcined petroleum coke, oil shale, tarsands, pitch, particulate carbon, and mixtures thereof. The liquidhydrocarbon fuel is selected from the group consisting of petroleumdistillate, gas oil, residual fuel oil, reduced crude, whole crude,asphalt, coal tar, coal oil, shale oil, tar sand oil, and mixturesthereof. Preferably, the liquid hydrocarbon fuel is scrubbing fluidwhich was used subsequently in the process and which containsparticulate carbon scrubbed from the effluent gas stream from the gasgenerator.

closed in said patent.

In the subject invention, either the first or second reactant slurrystream is passed into the reaction zone by way of the central nozzle ofthe triple orifice burner shown in FIG. 2 of the drawing for coassignedU.S. Pat. No. 3,705 ,108. Simultaneously, the other slurry stream ispassed through the outer coaxial annular nozzle that is disposed aboutan intermediate coaxial annular nozzle which in turn is disposed aboutsaid central nozzle. The third reactant stream comprising free-oxygencontaining gas is passed simultaneously through said intermediatecoaxial annular nozzle. The first and second reactant slurry streams arein liquid phase at a temperature in the range of about 40 to 700F. asthey pass through the burnerat a velocity at the burner tip in the rangeof about 1 ft. per sec. to 500 ft. per sec. and

preferably about 5 to 250 feet per second. The third reactant streamcomprising free-oxygen containing gas is at a temperature in the rangeof about 40 to 1,500F. as it passes through the burner at a velocity inthe burner tip in the range of about ft. per sec. to sonic velocity andpreferably about 200 to 450 ft. per sec. By

this arrangement, the free-oxygen containing gas emerges at the burnertip as a hollow conical shaped stream which is directed towards thelongitudinal axis of the burner, and which is interposed betwcen saidfirst and second slurry reactant stream. By this means the free-oxygencontaining stream may deeply penetrate the two slurry streams andprovide thorough mixing. The intermediate and outer annular channels areinclined slightly inwardly with respect to the longitudinal axis of theburner, making an angle in the range of about to 70. When the first andsecond slurry streams impinge together near the tip of the burner, thesolid particles in the two streams contact each other and are furtheredreduced in size. The intermediate high velocity jet stream of freeoxygen containing gas contacts the other two streams to form a fog ofminute solid particles. A substantially homogeneous and uniformdispersion of fine particles of solid carbonaceous fuel in atomizedliquid hydrocarbon fuel, H 0, and oxygen is produced. By this means thecombustion efficiency is improved, and there may be a reduction in theweight ratios steam to fuel, oxygen to fuel and total liquid hydrocarbonfuel to solid carbonaceous fuel.

The relative proportions of solid carbonaceous fuel, liquid hydrocarbonfuel,-water, and oxygen in the feedstreams to the gas generator arecarefully regulated to convert a substantial portion of the carbon, e.g.at least 80 wt. to carbon oxides e.g. CO and CO and to maintain anautogenous reaction zone temperature in the range of about 1,500 to3,500F., preferably in the range of about l,800 to 2,800F. The pressurein the reaction zone, is in the range of 1 to 250 atmospheres. The timein the reaction zone in seconds is the range of 0.5 to 50, andpreferably 1.0 to 10. The weight ratio of steam to total fuel (solidcarbonaceous fuel plus liquid hydrocarbon fuel) in the reaction zone isin the range of about 0.1 to 1.3, and preferably 0.2 to 0.50. The atomicratio of oxygen in the free oxygen containing gas to carbon in the totalfuel is in the range of about 0.6 to 1.6, and preferably 0.8 to 1.4. Itis common practice to express ratios in this manner as the denominatorofthe ratio is one and the numerator is the range specified e.g. 0.6 to1.6. i

0.1 to 3 parts by weight and preferably 0.5 to 1.5 parts by weight ofsaid solid carbonaceous fuel-liquid hydrocarbon fuel slurry areintroduced into the reaction zone per part by weight of solidcarbonaceous fuel-water slurry. i 1

About 0.8 to 12 parts by weight and preferably 2 to 12 parts by weightof total solid carbonaceous fuel are reacted in the gas generator perpart by weight of liquid hydrocarbon fuel.

The effluent gas stream from the reaction zone is split into two streamsfor cooling, cleaning, and for removing entrained solids. One gas streamis cooled in a waste-heat boiler and the other is cooled by quenching inwater in an quench vessel. If desired, acid gases i.e. H 5, COS, CO andmixtures thereof may be removed from the effluent gas stream. By thismeans fuel gas may be produced which may be burned without contaminatingthe environment. Also, the heatingvalue may be increased. Alternately,the product gas may be used as a synthesis gas feed which does notaffect sulfur-sensitive catalysts.

The effluent gas stream leaving the synthesis gas generator has thefollowing composition in mole H 8.0 to 60.0, CO 8.0 to 70.0, CO 1.0 to50.0, H O 2.0 to 50.0, CH 0 to 30.0, H S 0.0 to 1.0, COS 0.0 to 0.7

N 0.0 to 85.0, and A 0.0 to 2.0. Entrained in the effluent gas stream isabout 0.5 to 20.0 weight percent of particulate carbon (basis weight ofcarbon in the feed to the gas generator). As previously mentioned theeffluent gas stream is then split into two gas streams which areseparately cooled.

The first split stream of effluent gas comprising about 5 to 95 volumepercent and preferably about 75 to 95% of the total volume of effluentgas from the gas generator is cooled to a temperature in the range ofabout 200 to l,800F. and preferably from 400 to 600F. by indirect heatexchange with water in a waste heat boiler. Steam is simultaneouslyproduced at a temperature in the range of about 400 to 650F. Theparticulate carbon is scrubbed from the first split stream of effluentgas by conventional methods using a liquid hydrocarbon fuel scrubbingliquid. For example, as shown in coassigned U.S. Pat. No. 3,639,261 theprocess gas stream may be passed through a venturi or jet scrubber, suchas described in Perrys Chemical Engineers Handbook, Fourth Edition,McGraw Hill, Co., 1963, pages 18-55 to 56 and scrubbed with a scrubbingfluid selected from a liquid hydrocarbon fuel as previ- .ously describedor a dispersion of particulate carbon and liquid hydrocarbon fuel. Thenin a conventional oil knockout pot, the process gas stream is separatedfrom a dispersion of particulate carbon-liquid hydrocarbon fuelcontaining from about 1 to 20 wt. solids which is removed from thebottom of the knockout pot and mixed with ground solid Carboniferousfuel in a conventional grinding system. The aforesaid first slurryfeedstream is produced thereby and is introduced into the synthesis gasgenerator as previously described.

Any particulate carbon and other entrained solids such as a small amountof ash if any remaining in the process gas stream may be removed in asecond scrubbing stage. In such event, the process gas stream may bepassed through an orifice scrubber similar to that previously describedin the first scrubbing stage and scrubbed with water. Then in a waterknocko'ut pot, a clean product gas containing less than five mg ofparticulate carbon per SCF of gas is separated from a water dispersioncontaining from about 0.001 to 0.2 wt. of entrained solids. Thisdispersion may be subsequently concentrated in a manner to be furtherdescribed and used as a portion of the feed to the gas generator.Gaseous impurities may be removed from the process gas stream byconventional procedures.

The previously mentioned second split stream of effluent gas from thegas generator is cooled by direct quenching in water in a quench tanksuch as shown in coassigned U.S. Pat. No. 2,896,927. As the process gasstream bubbles through water maintained at a temperature in the range ofabout 50 to 450F. substantially all of the particulate carbon and otherentrained solids such as ash are scrubbed from the process gas streamand water is vaporized. Product gas saturated with water leaves near thetop of the quench tank. Optionally, this gas stream may be subjected towater-gas shift reaction to increase the H /COratio. H 0 and any gaseousimpurities may be then removed by conventional methods.

A water dispersion of particulate carbon and ash containing about 0.1 to2.0 wt. of solids from the bottom of the water quench tank, is mixedwith the dispersion of water and entrained solids e.g. particulatecarbon, from the previously described water knockout pot. Byconventional liquid-solids separation procedures e.g. settling,filtration, and centrifuge clarified water is separated from saiddispersion. For example, the dispersion may be passed into a settlingtank from which the following three streams are removed: a stream ofcoarse ash which is removed from the bottom of the tank, a waterdispersion stream; of,-fine ash and particulate carbon containing about1.0 to 20 weight percent of solids which is removed and passed into aconventional froth flotation process, and a clarified water stream whichis recycled to the water quench tank. A two-stage flotation system maybe used to resolve said water dispersion into separate streams of water,a stream of ash, and a concentrated particulate carbon-water slurrystream.

This concentrated particulate carbon-water slurry stream contains about10.0 to 40.0 weight percent of solids and is passed into a hold up tankfrom whence it provides liquid for slurry make-up or for wet grinding ofthe solid fuel. Ground make up solid carbonaceous fuel may be introducedin said mix and hold up tank. For example about 20 to 70 weight percentof solid fuel introduced into mix and hold up tank'comprises said solidcarbonaceous fuel make-up. A pumpable mixture of solid fuels and watercontaining 30 to 65 wt. solids from said mix and hold up tank ispreferably introduced into the gas generator as said first reactantslurry stream.

Optionally, the product gas stream from the water knockout pot or theproduct gas stream from the water quench tank may be submitted toadditional cleaning and conventional purification steps to remove anyremaining solids or at least one material from the group consisting of H0, CO CH H S, COS, A, and N DESCRIPTION OF THE DRAWING AND EXAMPLES Amore complete understanding of the invention may be had by reference tothe accompanying schematic drawing which shows in FIG. 1 the previouslydescribed process in detail. Quantities have been assigned to thevarious streams so that the following-description in Example 1 may bealso serve as an example of the subject invention.

EXAMPLE I On an hourly basis about 2,750 lbs..ofa ground solidcarbonaceous fuel-particulate carbon-water slurry feed in line 1 inliquid phase at a temperature of about 60F. are passed through the outerannular passage 2 and discharged into the reaction zone of synthesis gasgenerator 20 by way of converging outer annular orifice 3 of doubleannulus burner 4 at a velocity of 80 feet per second.

An enlarged vertical cross sectional view of burner 4 is shown in FIG.2. Double annulus burner 4 is more fully described in coassigned US.Pat. No. 3,705,108. Other features of the burner include concentricintermediate annular passage 5 which leads to concentric convergingintermediate annular discharge nozzle 6 and central conduit 7 whichleads to central nozzle or orifice 8. At the tip of the burner is hollowannular cooling chamber 9 through which cooling water is introduced byway of line 10. Tubing 11 through which cooling water is passed,encircles the outside barrel 12 of burner 4. By means of mounting plate13, burner 4 is attached to the upper flange of burner housing 14.Housing 14 is attached to flanged inlet 15 of vertical free-flownoncatalytic partial oxidation synthesis gas generator 20 having a 33cubic feet refractory lined reaction chamber 21.

The aforesaid solid carbonaceous fuel-particulate carbon-water slurry ispumped into line 1 by means of pump 22. This water slurry comes fromline 23 and mix and hold up tank 24. In Run No. 1, its composition inweight percent comprises Utah bituminous coal ground to a particle sizeso that 100% of the material passes through an ASTM El l SieveDesignation Standard 425 um and at least passes through an ASTM E l l-70Sieve Designation Standard 75 um 49.0, particulate carbon (producedsubsequently in the process) 1.0, and water 50.0. The materials whichare introduced into tank 24 and mixed together therein comprise groundmake-up Utah bituminous coal from line 25, and a concentrated dispersionof particulate carbon and water containing 10 weight percent of solidsfrom line 26. The Utah bituminous coal has the following ultimateanalysis in wt. C 78.9, H 7.5, N 1.1, S 1.1, O 7.2, and Ash 4.2. GrossHeating Value of the coal is 15,737 BTU/lb.

Simultaneously, about 4,125 lbs. of a ground solid carbonaceousfuel-particulate carbon-liquid hydrocarbon fuel slurry feed in line 30,in liquid phase, at a temperature of about 200F. are passed throughcentral conduit 7 of burner 4 and are discharged into the gas generatorreaction zone 21 through central nozzle 8 at a velocity of about 50 ft.per sec. The solid fuel-liquid hydrocarbon fuel slurry in line 30 forRun No. 1 is prepared by grinding together in conventional grindingsystem 31, 2,063 lbs. of Utah bituminous coal make-up (as previouslydescribed) from line 32, and 2,062 lbs. of a dispersion from line 33containing 0.4 wt. solids and comprising particulate carbon and 13.7 APICalifornia Reduced Crude make-up. The reduced crude has the followingultimate analysis in wt. C 85.8, H 11.26, S 1.98, O 0.11, and N 0.80,Ash 0.05, and a Heat of Combustion of 18,410 BTU per lb.

Simultaneously, about 5,417 lbs. of substantially pure oxygen (99.7 moleO feed in line 40 at a temperature of about F. are passed throughintermediate annular passage 5 and discharged into the gas generatorreaction zone 21 through converging intermediate annular nozzle 6 at avelocity of about 350 ft. per sec. By this arrangement of feedstreams, astream of substantially pure oxygen gas is discharged from the burnerand is interposed between the oil-slurry stream and the water-slurrystream. Upon discharge from burner 4, the three reactant streams contacteach other in the reaction zone with such force as to pulverize theparticles of bituminous coal. The slurry streams are atomized andthoroughly mixed with the oxygen stream.

Reaction takes place in reaction zone 21 of synthesis gas generator 20at an autogenous temperature of about 2,600F., and a pressure of about28 atmospheres. The residence time in the reaction zone is 2 seconds.241,400 standard cubic feet per hour (SCFH) of effluent stream ofsynthesis gas leave gas generator 20 by way of flanged exit 41 and line42 with the following composition in mole for Run No. 1: H 33.5, C053.1, CO 3.4, H 0 9.3, CH, 0.1, COS 0.02, 11 8' 0.2, N 0.3, A 0.1, and4.0 wt. of particulate carbon (basis weight of total carbon in thefeedstock to the gas generator).

The effluent stream of synthesis gas in line 42 is split from twostreams. The first split stream of effluent gas is passed through line43 and into waste heat boiler 44 where it is cooled to a temperature of630F. by indirect heat exchange with boiler feed water, entering throughline 45 at a temperature of 200F. and leaving through line 46 as steamat a temperature of 590F. The second split stream of effluent gas ispassed through line 47 and is cooled by direct quenching in water in aquench tank 48. Quench tank 48 is further described in coassigned US.Pat. No. 2,896,927. The product gas leaving quench tank 48 by way ofline 49 is saturated with water. Optionally, the product gas in line 49may be introduced into a conventional gas cleaning and purification zone(not shown in the drawing) where any remaining solids are removed andone or more gaseous impurities from the group CO H S, COS, A, CH. H 0,and N may be removed.

Particulate carbon in the aforesaid first split stream of effluent gasleaving waste heat boiler 44 by line 55, may be removed by passing saideffluent gas stream through a conventional orifice scrubber 56. Thescrubbing fluid which enters scrubber 56 by way of line 57 is a mixtureof California Reduced Crude make-up (as previously descirbed) whichenters the system through line 58 and a dispersion from line 59comprising particulate carbon and California Reduced Crude. Thisdispersion consists of about 0.4 wt. solids and is pumped by means ofpump 60 from the bottom of oil knockout pot 61 through lines 65, 66, and59. A portion of this dispersion is introduced into grinding system 31by way of line 33 as previously described. The process gas stream andscrubbing oil mixture leaving orifice scrubber 56 by way of line 62 ispassed into oil knockout pot 61 where the normally liquid dispersionseparates and is drawn off near the bottom as previously described. Theclean process gas stream leaves through line 68 near the top of oilknockout pot 61. Optionally, to remove any remainingparticulate carbon,the gas stream is passed through conventional orifice scrubber 69 andscrubbed with water from line 70. This water may include fresh make-upwater. The process gas stream is then introduced into knockout pot 75where clean product gas is removed through line 76 near the top ofknockout pot 75. The composition of this product gas stream is similarto that in line 49 with the exception that the water content is lessthan CO H 8, COS, A,. and N may be removed from the product gas streamin line 70 in a conventional gas purification zone not shown in thedrawing. A water dispersion containing 0.1 wt. solids substantiallycomprising particulate carbon and optionally some ash is removed throughline 77 at the bottom of pot 75.

The dispersion of water and solid particles in line 77 is mixed in line78 with the dispersion of water and solid particles containing 1.0 wt.solids e.g. particulate carbon and any ash leaving water quench tank 48by way of line 79. The mixture is passed into a conventional settlerunit 80. Clarified water is removed by way of line 81 and by means ofpump 82 is recycled to water quench tank 48 through line 83. A waterslurry of particulate carbon and any fine ash is removed from settlerunit 80 and is passed through line 84 into a conventional frothflotation unit 85. Any coarse ash may be removed from settler 80 through86. In flotation unit 85, any fine ash may be removed by way of line 87and water may be removed by way of line 88. Some of this water may betreated and discharged from the system for disposal while other portionsof this water may be recycled to quench tank 48 or to orifice scrubberor to both. A concentrated dispersion of particulate carbon and water isremoved by way of line 26 and is passed into mix and hold up tank 24, aspreviously described. 245 lbs. of ash or other solids may be removedfrom the system by way of lines 86 and 87.

To show the advantages of the subject process over systems employing asingle slurry feed stream, runs 2 and 3 which do not represent thesubject invention are shown below in Table III in comparison with theprocess of the subject invention (Run No. l). The operating conditions,and the amount of synthesis gas produced in all three runs are about thesame. In Run No. 2 the feed to the burner comprises: a coal-particulatecarbon-emulsion of liquid hydrocarbon fuel and water pumpable slurry;and a separate stream of free-oxygen containing gas. In Run No. 3 thefeed to the burner comprises: a coal-particulate carbon-water pumpableslurry; and a separate stream of free-oxygen containing gas.

TABLE III Run No Run No Run No.

Feed 1 3 Coal-particulate carbon-oil slurry, lbs. 4125 Coal-particulatecarbon-water slurry. lbs. 2750 11000 Coal-particulate carbon-oil andwater emulsion, lbs. slurry 7857 Free-Oxygen containing Gas (99.7 moleO1), SCF 64200 64200 65500 Effluent Gas Stream Leaving Gas Generator(line 42), Vol.

Hydrogen 33.49 30.88 24.64

Carbon Monoxide 53.08 47.05 32.39

Carbon Dioxide 3.40 5.86 10.55

Water 9.25 15.50 31.87

Methane .09 .08 .06

Carbonyl Sulfide .02 .01 .01

Hydrogen Sulfide .26 .22 .19

Nitrogen .33 .32 .49

Argon .08 .08 .06 Performance Oxygen Consumption, SCF/MSCF H,+CO net 306323 375 Water/Fuel ratio, lb/lb .25 .43 1.00 Total Solid Fuel/liquidhydrocarbon fuel, lb/lb 1.67 3.5 H,+CO, SCFH 209,000 198,300 174,100 SCFH,+CO/1b. fuel 38.0 36.1 31.7 SCF H,+CO/1b. solid fuel 60.8 50.5 31.7Unconverted Carbon, wt. percent 4.0 4.0 4.0

mole percent and the wt. of particulate carbon (basis weight of totalcarbon in the feedstock to the gas gener- From Table 111 it is readilyapparent that the performance characteristics for Run Number 1 whichrepresents the subject invention, are superior to that of the otherRuns. Significant economic savings are effected and a more stableoperation is attainable by the subject invention. This is evident by theincreased production of H -l-CO per lb. of fuel charged; the higherratio of total solid fuel/liquid hydrocarbon fuel; the lower oxygenconsumption per MSCF H -l-CO; and the reduced water to fuel ratio.

The process of the invention has been described generally and byexamples with reference to liquidsolid carboniferous fuel slurries andsynthesis gas of particular compositions for purposes of clarity andillustration only. It will be apparent to those skilled in the art fromthe foregoing that various modifications of the process and materialsdisclosed herein can be made without departure from the spirit of theinvention.

1 claim:

1. In the continuous manufacture of gaseous mixtures principallycomprising H and CO, and optionally containing at least one member ofthe group CO H O, CH N A, COS, and H 5 by the partial oxidation of ahydrocarbonaceous fuel with a free-oxygen containing gas in the presenceof a temperature moderator in a reaction zone free from packing andcatalyst of a freeflow gas generator, the improvement which comprisesintroducing into said reaction zone a continuous first slurry feedstreamcomprising a ground solid carbonaceous fuel and a liquid hydrocarbonfuel at a velocity in the range of about 1 to 500 feet per second;simultaneously introducing into said reaction zone so as to contact saidfirst slurry feedstream a continuous separate second slurry feedstreamcomprising a ground solid carbonaceous fuel and water at a velocity inthe range of about 1 to 500 feet per second; simultaneously introducinginto said reaction zone a continuous separate third stream comprising afree-oxygen containing gas interposed between said first and secondslurry feedstreams; and contacting and mixing said three streamstogether to form an atomized dispersion in which the ratio of atoms ofoxygen to atoms of carbon in the total fuel is in the range of about 0.6to 1.6, the weight ratio of H 0 to fuel is in the range of about 0.10 to1.3, and the weight ratio of total solid carbonaceous fuel to liquidhydrocarbon fuel is in the range of about 0.8 to 12, and reacting saidatomized dispersion in said reaction zone at a temperature in the rangeof about l,500 to 3,500F., and a pressure in the range of about 1 to 250atmospheres.

2. The process of claim 1 wherein said first slurry stream comprises0.30 to 0.65 parts by weight of a ground solid carbonaceous fuelselected from the group consisting of petroleum coke, coal, particulatecarbon, coal char, coke from coal, oil shale, tar sands, pitch andmixtures thereof for each part by weight of liquid hydrocarbon fuelselected from the group consisting of fuel oil, residual fuel oil,reduced crude oil, whole crude oil, coal oil, shale oil, gasoline,kerosene, naphtha, gas oil fractions of petroleum distillate, benzene,toluene, hexane, heptane cyclohexane, tetralin, decalin and mixturesthereof; and wherein said second slurry stream comprises 0.30 to 0.65parts by weight of said solid carbonaceous fuel for each part by weightof water.

3. The process of claim 1 provided with the additional steps of 1splitting the effluent gas stream from said reaction zone into first andsecond process gas streams; (2) cooling said first process gas streamfrom (1) by indirect heat exchange with water to produce steam in awaste heat boiler; (3) simultaneously cooling and scrubbing said secondprocess gas stream from (1 to remove entrained solids by immersion inwater in a quench tank; (4) scrubbing the effluent gas stream from thewaste-heat boiler in (2) with scrubbing oil to remove entrained solidsand to produce a product gas stream principally comprising H and CO andcontaining less than 10 mole H 0; and (5) removing the effluent gasstream from the quench tank in (3) to produce a product gas streamsaturated with water and principally comprising H and CO.

4. A process for the production of fuel gas or synthesis gas comprisingintroducing into the reaction zone free from packing and catalyst ofafree-flow gas generator a continuous first slurry feedstream comprisinga solid carbonaceous fuel and a liquid hydrocarbon fuel at a velocity inthe range of about 1 to 500 feet per second, wherein said first slurrystream comprises 0.30 to 0.65 parts by weight of a ground solidcarbonaceous fuel selected from the group consisting of petroluem coke,coal, particulate carbon, coal char, coke from coal, oil shale, tarsands, pitch, and mixtures thereof for each part by weight of liquidhydrocarbon fuel selected from the group consisting of fuel oil,residual fuel oil, reduced crude oil, whole crude oil, coal oil, shaleoil, gasoline, kerosene, naphtha, gas oil fractions of petroleumdistillate, benzene, toluene, hexane, heptane, cyclohexane, tetralin,decalin and mixtures thereof; simultaneously introducing into saidreaction zone so as to contact said first slurry feedstream a continuousseparate second slurry feedstream comprising a solid carbonaceous fueland water at a velocity in the range of about 1 to 500 feet per second,and wherein said second slurry stream comprises 0.3 to 0.65 parts byweight of said ground solid carboniferous fuel for each part by weightof water; simultaneously introducing into said reaction zone acontinuous separate third feedstream comprising a free-oxygen containinggas interposed between said first and second slurry feedstreams, andcontacting and mixing said three feedstreams together to form anatomized dispersion in which the ratio of atoms of oxygen to atoms ofcarbon in the total fuel is in the range of about 0.6 to 1.6, the weightratio of H 0 to fuel is in the range of about 0.10 to 1.3, and theweight ratio of total solid carbonaceous fuel to liquid hydrocarbon fuelis in the range of about 0.8 to 12, and reacting said atomizeddispersion in said reaction zone at a temperature in the range of about1,500 to 3,500F., a pressure in the range of about 1 to 250 atmospheres,and for a residence time of 1 to 10 seconds; splitting the effluentgaseous stream from said reaction zone into first and second splitprocess gas streams; cooling said first split process gas stream byindirect heat exchange with water in a waste heat boiler to producesteam; scrubbing with liquid hydrocarbon fuel or a dispersion ofparticulate carbon and liquid hydrocarbon fuel the effluent gas streamfrom said waste heat boiler to remove entrained solid particles,separating a dispersion of particulate carbon and liquid hydrocarbonfuel, and separating a first product gas stream principally comprising Hand CO and containing at least one member of the group CO H O, CH N A,COS, and H 8; mixing a portion of said dispersion of particulate carbonand liquid hydrocarbon fuel with make-up solid carboniferous fuel toproduce said first slurry feedstream to the gas generator; separating atleast one member of the group CO H O, CH N A, COS, and H 8 from saidfirst product gas stream in a gas purification zone; and simultaneouslycooling and scrubbing to remove entrained solid particles from saidsecond split process gas stream by immersion in water in a quench zone,removing a second product gas stream from said quench zone similar tosaid first product gas stream but saturated with H and substantiallyfree from entrained solid particles; removing a dispersion of solidparticles and water from said quench zone and separating therefrom aconcentrated particulate carbon-water dispersion, and mixing said groundsolid carbonaceous fuel with said concentrated dispersion of particulatecarbon-water to produce said second slurry feedstream to the gasgenerator.

5. The process of claim 4 provided with the additional steps prior tosaid gas purification zone of scrubbing said first product gas streamwith water to remove any remaining entrained solids; separating a cleanfirst 14 product gas stream, separating a dispersion of entrained solidsand water and mixing said dispersion with said dispersion "of solidparticles and water from said quench zone.

6. The process of claim 5 provided with the additional steps ofintroducing said mixed dispersion of solid particles and water into asettling zone; withdrawing from said settling zone a separate stream ofclear water and recycling same to said quench zone, and a separatestream of coarse ash, and a separate stream of particulate carbon andline ash dispersed in water; introducing said water dispersion ofparticulate carbon and fine ash into a froth flotation zone and removingtherefrom three separate streams comprising water, ash, and saidconcentrated dispersion of particulate carbon-water.

1. IN THE CONTINUOUS MANUFACTURE OF GASEOUS MIXTURES PRINCIPALLYCOMPRISING H2 AND CO, AND OPTIONALLY CONTAINING AT LEAST ONE MEMBER OFTHE GROUP CO2, H2O, CH4, N2, A, COS, AND H2S BY THE PARTIAL OXIDATION OFA HYDROCARBONACEOUS FUEL WITH A FREE-OXYGEN CONTAINING GAS IN THEPRESENCE OF A TEMPERATURE MODERATOR IN A REACTION ZONE FREE FROM PACKINGAND CATALYST OF A FREE-FLOWING GAS GENERATOR, THE IMPROVEMENT WHICHCOMPRISES INTRODUCING INTO SAID REACTION ZONE A CONTINUOUS FIRST SLURRYFEEDSTREAM COMPRISING A GROUND SOLID CARBONACEOUS FUEL AND A LIQUIDHYDROCARBON FUEL AT A VELOCITY IN THE RANGE OF ABOUT 1 TO 500 FEET PERSECOND; SIMULTANEOUSLY INTRODUCING INTO SAID REACTION ZONE SO AS TOCONTACT SAID FIRST SLURRY FEEDSTREAM A CONTINUOUS SEPARATE SECOND SLURRYFEEDSTREAM COMPRISING A GROUND SOLID CARBONACEOUS FUEL AND WATER AT AVELOCITY IN THE RANGE OF ABOUT 1 TO 500 FEET PER SECOND; SIMULTANEOUSLYINTRODUCING INTO SAID REACTION ZONE A CONTINUOUS SEPARATE THIRD STREAMCOMPRISING A FREE-OXYGEN CONTAINING GAS INTERPOSED BETWEEN SAID FIRSTAND SECOND SLURRY FEEDSTREAMS; AND CONTACTING AND MIXING SAID THREESTREAMS TOGETHER TO FORM AN ATOMIZED DISPERSION IN WHICH THE RATIO OFATOMS OF OXYGEN TO ATOMS OF CARBON IN THE TOTAL FUEL IS IN THE RANGE OFABOUT 0.6 TO 1.6, THE WEIGHT RATIO OF H2O TO FUEL IS IN THE RANGE OFABOUT 0.10 TO 1.3, AND THE WEIGHT RATIO OF TOTAL SOLID CARBONACEOUS FUELTO LIQUID HYDROCARBON FUEL IS IN THE RANGE OF ABOUT 0.8 TO 12, ANDREACTING SAID ATOMIZED DISPERSION IN SAID REACTION ZONE AT A TEMPERATUREIN THE RANGE OF ABOUT 1,500* TO 3,500*F., AND A PRESSURE IN THE RANGE OFABOUT 1 TO 250 ATMOSPHERES.
 2. The process of claim 1 wherein said firstslurry stream comprises 0.30 to 0.65 parts by weight of a ground solidcarbonaceous fuel selected from the group consisting of petroleum coke,coal, particulate carbon, coal char, coke from coal, oil shale, tarsands, pitch and mixtures thereof for each part by weight of liquidhydrocarbon fuel selected from the group consisting of fuel oil,residual fuel oil, reduced crude oil, whole crude oil, coal oil, shaleoil, gasoline, kerosene, naphtha, gas oil fractions of petroleumdistillate, benzene, toluene, hexane, heptane cyclohexane, tetralin,decalin and mixtures thereof; and wherein said second slurry streamcomprises 0.30 to 0.65 parts by weight of said solid carbonaceous fuelfor each part by weight of water.
 3. The process of claim 1 providedwith the additional steps of (1) splitting the effluent gas stream fromsaid reaction zone into first and second process gas streams; (2)cooling said first process gas stream from (1) by indirect heat exchangewith water to produce steam in a waste heat boiler; (3) simultaneouslycooling and scrubbing said second process gas stream from (1) to removeentrained solids by immersion in water in a quench tank; (4) scrubbingthe effluent gas stream from the waste-heat boiler in (2) with scrubbingoil to remove entrained solids and to produce a product gas streamprincipally comprising H2 and CO and containing less than 10 mole % H2O;and (5) removing the effluent gas stream from the quench tank in (3) toproduce a product gas stream saturated with water and principallycomprising H2 and CO.
 4. A process for the production of fuel gas orsynthesis gas comprising introducing into the reaction zone free frompacking and catalyst of a free-flow gas generator a continuous firstslurry feedstream comprising a solid carbonaceous fuel and a liquidhydrocarbon fuel at a velocity in the range of about 1 to 500 feet persecond, wherein said first slurry stream comprises 0.30 to 0.65 parts byweight of a ground solid carbonaceous fuel selected from the groupconsisting of petroluem coke, coal, particulate carbon, coal char, cokefrom coal, oil shale, tar sands, pitch, and mixtures thereof for eachpart by weight of liquid hydrocarbon fuel selected from the groupconsisting of fuel oil, residual fuel oil, reduced crude oil, wholecrude oil, coal oil, shale oil, gasoline, kerosene, naphtha, gas oilfractions of petroleum distillate, benzene, toluene, hexane, heptane,cyclohexane, tetralin, decalin and mixtures thereof; simultaneouslyintroducing into said reaction zone so as to contact said first slurryfeedstream a continuous separate second slurry feedstream comprising asolid carbonaceous fuel and water at a velocity in the range of about 1to 500 feet per second, and wherein said second slurry stream comprises0.3 to 0.65 parts by weight of said ground solid carboniferous fuel foreach part by weight of water; simultaneously introducing into saidreaction zone a continuous separate third feedstream comprising afree-oxygen containing gas interposed between said first and secondslurry feedstreams, and contacting and mixing said three feedstreamstogether to form an atomized dispersion in which the ratio of atoms ofoxygen to atoms of carbon in the total fuel is in the range of about 0.6to 1.6, the weight ratio of H2O to fuel is in the range of about 0.10 to1.3, and the weight ratio of total solid carbonaceous fuel to liquidhydrocarbon fuel is in the range of about 0.8 to 12, and reacting saidatomized dispersion in said reaction zone at a temperature in the rangeof about 1,500* to 3,500*F., a pressure in the range of about 1 to 250atmospheres, and for a residence time of 1 to 10 seconds; splitting theeffluent gaseous stream from said reaction zone into first and secondsplit process gas streams; cooling said first split process gas streamby indirect heat exchange with water in a waste heat boiler to producesteam; scrubbing with liquid hydrocarbon fuel or a dispersion ofparticulate carbon and liquid hydrocarbon fuel the effluent gas streamfrom said waste heat boiler to remove entrained solid particles,separating a dispersion of particulate carbon and liquid hydrocarbonfuel, and separating a first product gas stream principally comprisingH2 and CO and containing at least one member of the group CO2, H2O, CH4,N2, A, COS, and H2S; mixing a portion of said dispersion of particulatecarbon and liquid hydrocarbon fuel with make-up solid carboniferous fuelto produce said first slurry feedstream to the gas generator; separatingat least one member of the group CO2, H2O, CH4, N2, A, COS, and H2S fromsaid first product gas stream in a gas purification zone; andsimultaneously cooling and scrubbing to remove entrained solid particlesfrom said second split process gas stream by immersion in water in aquench zone, removing a second product gas stream from said quench zonesimilar to said first product gas stream but saturated with H2O andsubstantially free from entrained solid particles; removing a dispersionof solid particles and water from said quench zone and separatingtherefrom a concentrated particulate carbon-water dispersion, and mixingsaid ground solid carbonaceous fuel with said concentrated dispersion ofparticulate carbon-water to produce said second slurry feedstream to thegas generator.
 5. The process of cLaim 4 provided with the additionalsteps prior to said gas purification zone of scrubbing said firstproduct gas stream with water to remove any remaining entrained solids;separating a clean first product gas stream, separating a dispersion ofentrained solids and water and mixing said dispersion with saiddispersion of solid particles and water from said quench zone.
 6. Theprocess of claim 5 provided with the additional steps of introducingsaid mixed dispersion of solid particles and water into a settling zone;withdrawing from said settling zone a separate stream of clear water andrecycling same to said quench zone, and a separate stream of coarse ash,and a separate stream of particulate carbon and fine ash dispersed inwater; introducing said water dispersion of particulate carbon and fineash into a froth flotation zone and removing therefrom three separatestreams comprising water, ash, and said concentrated dispersion ofparticulate carbon-water.